HFO-1234ze and HFO-1234yf compositions and processes for producing and using the compositions

ABSTRACT

A fluoropropene composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane wherein the 2,3,3,3-tetrafluoropropene being present in an amount of 0.001 to 1.0%. A method of producing the fluoropropene, methods for using the fluoropropene and the composition formed are also disclosed.

This Application represents a national filing under 35 U.S.C. 371 ofInternational Application No. PCT/US2019/057999 filed Oct. 25, 2019, andclaims benefit of Provisional Application No. 62/750,991, filed on Oct.26, 2018. The disclosure of Application No. 62/750,991 is herebyincorporated by reference.

FIELD OF THE INVENTION

The present invention relates to tetrafluoropropene compositions andmethods for making and using the compositions and, in particular, to amethod for producing and using a product comprising1,3,3,3-tetrafluoropropene (HFO-1234ze) and 2,3,3,3-tetrafluoropropene(HFO-1234yf) prepared from 1,1,1,3,3-pentafluoropropane (HFC-245fa).

BACKGROUND OF THE INVENTION

The fluorocarbon industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for manyapplications has been the commercialization of hydrofluorocarbon (HFC)compounds for use as refrigerants, solvents, fire extinguishing agents,blowing agents and propellants. These new compounds, such as HFCrefrigerants, HFC-134a and HFC-125 being the most widely used at thistime, have zero ozone depletion potential and thus are not affected bythe current regulatory phase-out as a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is anotherenvironmental concern in many of these applications. Thus, there is aneed for compositions that meet both low ozone depletion standards aswell as having low global warming potentials. Certain hydrofluoroolefincompositions are believed to meet both goals. Thus, there is also a needfor economical manufacturing processes that provide these compositions.

HFO-1234ze (CF₃CH═CHF) and HFO-1234yf (CF₃CF═CH₂), both having zeroozone depletion and low global warming potential, have been identifiedas potential refrigerants. U.S. Pat. No. 7,862,742 disclosescompositions comprising HFO-1234ze and HFO-1234yf. U.S. Pat. No.9,302,962 discloses methods for making HFO-1234ze. The disclosures ofU.S. Pat. Nos. 7,862,742 and 9,302,962 are hereby

Catalytic dehydrofluorination of HFC-245fa in general produces a mixtureof both the E-isomer as well as the Z-isomer of HFC-1234ze. Depending onthe particular catalyst chosen, the amount of the Z-isomer can varybetween 15% to 23%. Dehydrofluorination in the liquid phase usingaqueous solutions of caustic or other strong bases also produces mixtureof both isomers. Although the ratio of the two isomers can be shiftedsomewhat by temperature, about 13% to about 15% of the Z-isomer istypically formed. As the E-isomer is the most useful for refrigerationapplications, after separation of the E-isomer from the Z-isomer, theZ-isomer is typically either isomerized to the E-isomer in a separatestep or converted back to 245fa through addition of hydrogen fluoride.Both alternatives require additional steps which add cost.

There is a need in this art for a process that can produce nearazeotropic compositions of HFO-1234ze and HFO-1234yf that minimizes oreliminates the need for purification or separation steps for removingexcess quantities of HFO-1234yf. In particular, there is a need in thisart for an economical process that produces near azeotropic compositionscomprising HFO-1234ze and greater than zero and less than about 1 weightpercent HFO-1234yf.

BRIEF DESCRIPTION OF THE INVENTION

Described is a fluoropropene composition comprisingZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene,2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane.The 2,3,3,3-tetrafluoropropene being present in an amount of 0.001 to1.0 mol %.

In addition, the present disclosure includes a method of producing amixture of a fluoropropene of formula CF₃CH═CHF and a fluoropropene offormula CF₃CF═CH₂, comprising contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr2O3 or Cr/Ni on fluorinatedalumina, in the presence of an oxygen containing gas, to form a mixturecomprising Z-1,3,3,3-tetrafluoropropane, E-1,3,3,3,-tetrafluoropropene,2,3,3,3-tetrafluoropropene, and optionally unreacted1,1,1,3,3-pentafluoropropane. One embodiment the inventive methodproduces a useful composition without the need for purification orseparation steps including steps for removing excess quantities of2,3,3,3-tetrafluoropropene (HFO-1234yf).

Further still, the present disclosure includes fluoropropenecompositions formed from the method of contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr2O3 or Cr/Ni on fluorinatedalumina, optionally in the presence of an oxygen containing gas.

In one embodiment, the inventive process produces a near azeotropiccomposition comprising HFO-1234ze(E) and HFO-1234yf and the azeotropiccomposition is useful as a refrigerant.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.01 to 1.0 mol %.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.1 to 0.9 mol %.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.2 to 0.4 mol %.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.3 to 0.4 mol %.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition additionally optionally comprises one or moreof R-143a, R-152a, TFP (trifluoropropyne), R-1233xf, R-1233zd(E), orR-1233zd(Z).

One embodiment relates to any combination of the foregoing wherein thesum total of the amounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E),and R-1233zd(Z) is between 0.001 mole percent and 2 mole percent, basedon the total fluoropropene composition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition includes R-1233zd(E) in an amount of 0.7 molepercent to 1.15 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition includes R-1233zd(Z) in an amount of 0.05 molepercent to 0.25 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition includes R-143a in an amount of 0.05 molepercent to 0.25 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition optionally comprises one or more of 1224yd,1224zc, 1326mxz, 113, 32, 23, trifluoro propyne, 356mff, 1326mxz,HFC-245fa and HFC-245cb.

One embodiment relates to any combination of the foregoing wherein thesum total of the amounts 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropyne, 356mff, 1326mxz, HFC-245fa and HFC-245cb is between 0.001 molepercent and 2 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thecomposition is near azeotropic.

Another embodiment of the invention relates to a method of producing amixture of a fluoropropene of formula CF₃CH═CHF and a fluoropropene offormula CF₃CF═CH₂, comprising:

-   -   contacting a mixture of 1,1,1,3,3-pentafluoropropane and        Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst        comprising at least one catalyst selected from the group        consisting of fluorinated Cr₂O₃ or Cr/Ni on fluorinated alumina,        in the presence of an oxygen containing gas, to form a mixture        comprising Z-1,3,3,3-tetrafluoropropene,        E-1,3,3,3,-tetrafluoropropene, 2,3,3,3-tetrafluoropropene,        hydrogen fluoride, and optionally unreacted        1,1,1,3,3-pentafluoropropane        wherein the mixture includes 0.01% to 1.00%        2,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein said mixture of 1,1,1,3,3-pentafluoropropane andZ-1,3,3,3-tetrafluoropropene comprises at least 7% by weightZ-1,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein said mixture of 1,1,1,3,3-pentafluoropropane andZ-1,3,3,3-tetrafluoropropene comprises at least 10% by weightZ-1,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein at least 94% by weight of the1,1,1,3,3-pentafluoropropane is converted to E-isomer of1,3,3,3-tetrafloropropene.

One embodiment of the invention relates to any combination of theforegoing wherein at least 98% by weight of the1,1,1,3,3-pentafluoropropane is converted to E-isomer of1,3,3,3-tetrafloropropene.

One embodiment of the invention relates to any combination of theforegoing and further comprising recoveringZ-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, andrecycling Z-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane back tostep (a).

One embodiment of the invention relates to any combination of theforegoing wherein said hydrogen fluoride produced in step (a) isseparated and recovered.

One embodiment of the invention relates to any combination of theforegoing wherein said oxygen containing gas is oxygen, or air.

One embodiment of the invention relates to any combination of theforegoing wherein the mixture includes 0.1 to 0.5 mol %2,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein the mixture includes 0.2 to 0.4 mol %2,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein the mixture includes 0.3 to 0.4 mol %2,3,3,3-tetrafluoropropene.

Another embodiment of the invention relates to any combination of theforegoing methods and to a fluoropropene composition produced by thesemethods.

One embodiment of the invention relates to a process for transferringheat, comprising:

providing an article;

contacting the article with a heat transfer media;

wherein the heat transfer media comprises the fluoropropene compositionof any combination of the foregoing embodiments and including a nearazeotropic composition produced by the inventive method.

One embodiment of the invention relates to a process for treating asurface, comprising:

providing a surface;

contacting the surface with a treatment composition;

wherein the surface includes a treatable material deposited thereon; andwherein the treatment composition comprises the fluoropropenecomposition of any combination of the foregoing embodiments.

One embodiment of the invention relates to any combination of theforegoing wherein the treatment composition substantially dissolves thetreatable material.

One embodiment of the invention relates to a process for forming acomposition comprising:

providing a solute; contacting the solute with a solvent;

wherein the solvent comprises the fluoropropene composition of any ofthe foregoing embodiments.

Another embodiment of the invention relates to a refrigeration system,comprising:

an evaporator; a condenser;

a compressor; an expansion device;

and a heat transfer media;

wherein the heat transfer media comprises the fluoropropene compositionof any combination of the foregoing embodiments and including a nearazeotropic composition produced by the inventive method.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims. The various embodiments ofthe invention can be used alone or in combinations with each other.Other features and advantages of the present invention will be apparentfrom the following more detailed description of the preferredembodiment, which illustrate, by way of example, the principles of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

Described is a method of producing a mixture of a fluoropropene offormula CF₃CH═CHF and a fluoropropene of formula CF₃CF═CH₂, comprisingcontacting a mixture of 1,1,1,3,3-pentafluoropropane andZ-,1,3,3,3-tetrafluoropropene in the gas phase with a catalystcomprising at least one catalyst selected from the group consisting offluorinated Cr₂O₃ or Cr/Ni on fluoride alumina, optionally in thepresence of an oxygen containing gas, to form a mixture comprisingZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene,2,3,3,3-tetrafluoropropene, and, optionally, unreacted1,1,1,3,3-pentafluoropropane.

Certain dehydrofluorination reactions are well known in the art. Thedehydrofluorination of HFC-245fa has been particularly studied. Both gasphase and liquid phases processes are known. 1,3,3,3-tetrafluoropropene(HFO-1234ze) exists as both a Z-isomer and an E-isomer about the doublebond. Both gas phase and liquid phase processes are known to produce amixture of both the Z- and E-isomers, with the E-isomer predominating.The selectivity for the production of the Z-isomer can vary from about10% to about 23%, depending on the temperature, and choice of catalyst.The boiling point of the E-isomer at 1 atm is about −19° C., while theboiling point of the Z-isomer is about 9° C. For many uses, the E-isomeris preferred. So as to minimize yield losses in the form of thegenerally unwanted Z-isomer, it becomes necessary to either add anisomerization step to isomerize the Z-isomer to the E-isomer, or add afluorination step to convert HFO-1234ze(Z) back to HFC-245fa.

The dehydrofluorination reaction according to embodiments of the presentdisclosure may result in azeotropic and, in most cases, near azeotropiccompositions of HFO-1234ze(E) and HFO-1234yf that minimizes oreliminates the need for purification or separation steps for removingexcess quantities of HFO-1234yf. By azeotropic compositions it is meanta constant-boiling mixture of two or more substances that behave as asingle substance. One manner to characterize an azeotropic compositionis that the vapor produced by partial evaporation or distillation of aliquid has the same composition as the liquid from which it isevaporated or distilled (i.e., the mixture distills/refluxes withoutcompositional change). Constant-boiling compositions are characterizedas azeotropic because they exhibit either a maximum or minimum boilingpoint, as compared with that of the non-azeotropic mixture of the samecompounds. An azeotropic composition will not fractionate within arefrigeration or air conditioning system during operation. Additionally,an azeotropic composition will not fractionate upon leakage from arefrigeration or air conditioning system. In the situation where onecomponent of a mixture is flammable, fractionation during leakage couldlead to a flammable composition either within the system or outside ofthe system.

By a near-azeotropic composition it is meant to refer to a substantiallyconstant boiling liquid admixture of two or more compounds that behaveessentially as a single substance. One manner to characterize anear-azeotropic composition is that the vapor produced by partialevaporation or distillation of a liquid has substantially the samecomposition as the liquid from which it was evaporated or distilled,that is, the admixture distills/refluxes without substantiallycompositional change. Another manner to characterize a near-azeotropiccomposition is that the bubble point vapor pressure and the dew pointpressure of the composition at a particular temperature aresubstantially the same. In particular, a composition of the invention isnear-azeotropic if, after 50 weight percent (50%) of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure, between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed, isless than about 10 percent (10%).

In accordance with one embodiment of the instant invention, theinventive near azeotropic compositions have a flammability rating of A2Las determined by ASHRAE Standard 34 and ASTM E681-09.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims.

Certain, dehydrofluorinations are known in the art, and are preferablyconducted in the vapor phase. The dehydrofluorination reaction may beconducted in any suitable reaction vessel or reactor, but it shouldpreferably be constructed from materials which are resistant to thecorrosive effects of hydrogen fluoride, such as nickel and its alloys,including Hastelloy, Monel, and Inconel, or vessels lined withfluoropolymers. These may be a single tube, or multiple tubes packedwith a dehydrofluorination catalyst.

Useful catalysts for the process include chromium-based catalysts suchas fluorinated chromium oxide, which catalyst may either be unsupported,or supported on a support such as activated carbon, graphite, fluoridegraphite, or alumina fluoride. The chromium catalyst may either be usedalone, or in the presence of a co-catalyst selected from nickel, cobalt,manganese or zinc salt. In one embodiment, a chromium catalyst is highsurface area chromium oxide, or chromium/nickel on alumina fluoride(Cr/Ni/AlF₃), the preparation of which is reported in European PatentEP486,333. In another embodiment, the catalyst is fluorinated Guignet'sgreen catalyst. Additional suitable catalysts include, but are notlimited to, JM 62-2 (chrome catalyst available from Johnson Matthey),LV(chrome catalyst available from Chemours), JM-62-3 (chrome catalystavailable from Johnson Matthey), and Newport Chrome (chrome catalystavailable from Chemours). The chromium catalysts are preferablyactivated before use, typically by a procedure whereby the catalyst isheated to from 350° C. to 400° C. under a flow of nitrogen for a periodof time, after which the catalyst is heated under a flow of HF andnitrogen or air for an additional period of time.

In one embodiment, the Guignet's Green of the fluoride-activatedGuignet's Green catalyst used in the present invention is made byreacting (fusing) boric acid with alkali metal dichromate at 500° C. to800° C., followed by hydrolysis of the reaction product, whereby saidGuignet's Green contains boron, alkali metal, and water of hydration.The usual alkali metal dichromates are the Na and/or K dichromates. Thereaction is typically followed by the steps of cooling the reactionproduct in air, crushing this solid to produce a powder, followed byhydrolysis, filtering, drying, milling and screening. The Guignet'sGreen is bluish green, but is known primarily as a green pigment,whereby the pigment is commonly referred to as Guignet's Green. Whenused as a catalyst, it is also referred to as Guignet's Green asdisclosed in U.S. Pat. No. 3,413,363. In U.S. Pat. No. 6,034,289, Cr₂O₃catalysts are disclosed as preferably being in the alpha form, andGuignet's Green is also disclosed as a commercially available greenpigment having the composition: Cr₂O₃ 79-83%, H₂O 16-18%, B₂O₅ 1.5 to2.7% (sentence bridging cols. 2 and 3) that can be converted to thealpha form (col. 3, I. 3). U.S. Pat. No. 7,985,884 acknowledges thepresence of alkali metal in the Guignet's Green in the composition ofGuignet's Green disclosed in Example 1: 54.5% Cr, 1.43% B, 3,400 ppm Na,and 120 ppm K.

The physical shape of the catalyst is not critical and may, for example,include pellets, extrudates, powders, or granules. The fluorideactivation of the catalyst is preferably carried out on the final shapeof the catalyst.

In one embodiment, the instant invention relates to feeding a mixture ofHFC-245fa and at least about 10% by weight of the Z-isomer of HFO-1234zeto a dehydrofluorination reactor in the presence of an oxygen containinggas in order to suppress the formation of additional Z-isomer so thatthe HFC-245fa converted by dehydrofluorination produces substantiallyonly E-HFO-1234ze and HFO-1234yf. Feeding less than about 10% willresult in some suppression of the formation of additional Z-1234ze.Feeding greater than about 10% by weight of Z-1234ze simply results inthe presence of additional material which must be separated andrecycled. The amount of Z-1234ze which is necessary to suppress thefurther formation of Z-isomer product is dependent to some extent onconversion. At 70% conversion of 245fa, about 10-11% Z-isomer in thefeed is required. At 80% conversion, about 13% Z-isomer in the feed isrequired.

In one embodiment, the reaction vessel can be held at a temperature ofbetween 200° C. and 375° C. In another embodiment, the reaction vesselcan be held at a temperature of between 250° C. and 350° C. In yetanother embodiment, the reaction vessel can be held at a temperature ofbetween 275° C. and 325° C.

The reaction pressure can be subatmospheric, atmospheric, orsuperatmospheric. In one embodiment, the reaction is conducted at apressure of from 14 psig to about 100 psig. In another embodiment, thereaction is conducted at a pressure of from 14 psig to about 60 psig. Inyet another embodiment, the reaction is conducted at a pressure of from40 psig to about 85 psig. In yet another embodiment, the reaction isconducted at a pressure of from 50 psig to 75 psig. In general,increasing the pressure in the reactor above atmospheric pressure willact to increase the contact time of the reactants in the process. Longercontact times will necessarily increase the degree of conversion in aprocess, without having to increase temperature.

Depending on the temperature of the reactor, and the contact time, theproduct mixture from the reactor will contain varying amounts ofunreacted HFC-245fa. In certain embodiment, E-1,3,3,3-tetrafluoropropeneand HFO-1234yf may be separated from the Z-1,3,3,3-tetrafluoropropene,hydrogen fluoride, and any unreacted HFC-245fa, which are then recycledback to the reactor with additional HFC-245fa. Hydrogen fluoride may beremoved by scrubbing, by passing the reactor effluent through a solutionof aqueous caustic, or hydrogen fluoride may be removed by distillation.In particularly suitable embodiments, the composition formed from theprocess of the present disclosure includes both1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and2,3,3,3-tetrafluoropropene (HFO-1234yf), which are not separated.

In one embodiment, the reactor feed is preheated in a vaporizer to atemperature of from about 30° C. to about 100° C. In another embodiment,the reactor feed is preheated in a vaporizer to a temperature of fromabout 30° C. to about 80° C.

In some embodiments, an inert diluent gas is used as a carrier gas forthe hydrochlorofluoropropane. In one embodiment, the carrier gas isselected from nitrogen, argon, helium, or carbon dioxide.

In one embodiment, the product mixture includes (on a mol basis) between0.01% to 1.00% HFO-1234yf, alternatively between 0.05% to 0.95%HFO-1234yf, alternatively between 0.10% to 0.90% HFO-1234yf,alternatively between 0.20% to 0.80% HFO-1234yf, alternatively between0.01% to 0.20% HFO-1234yf, alternatively between 0.10% to 0.30%HFO-1234yf, alternatively between 0.20% to 0.40% HFO-1234yf,alternatively between 0.30% to 0.50% HFO-1234yf, alternatively between0.30% to 0.40% HFO-1234yf, alternatively between 0.40% to 0.60%HFC-1234yf, alternatively between 0.50% to 0.70% HFO-1234yf,alternatively between 0.60% to 0.80% HFO-1234yf, alternatively between0.70% to 0.70% HFO-1234yf, alternatively between 0.80% to 1.00%HFO-1234yf.

In some embodiments, the fluoropropene composition additionallyoptionally comprises one or more of R-143a, R-152a, TFP, R-1233xf,R-1233zd(E), or R-1233zd(Z). In some embodiments, the sum total of theamounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z)is between 0.01 mole percent and 2 mole percent, based on the totalfluoropropene composition. In one embodiment, the fluoropropenecomposition includes R-1233zd(E) in an amount of 0.7 mole percent to1.15 mole percent, based on the total heat transfer media. In oneembodiment, the fluoropropene composition includes R-1233zd(Z) in anamount of 0.05 mole percent to 0.25 mole percent, based on the totalheat transfer media. In one embodiment, the fluoropropene compositionincludes R-143a in an amount of 0.05 mole percent to 0.25 mole percent,based on the total fluoropropene composition.

In other embodiments, the fluoropropene composition optionally comprisesone or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoro propyne,356mff, 1326mxz, HFC-245fa and HFC-245cb.

In one particular embodiment, the sum total of the amounts 1224yd,1224zc, 1326mxz, 113, 32, 23, trifluoro propyne, 356mff, 1326mxz,HFC-245fa and HFC-245cb is between 0.001 mole percent and 2 molepercent, based on the total fluoropropene composition.

The fluoropropene composition may be useful in various applications. Inan embodiment, the fluoropropene composition may be used as arefrigerant. In some embodiments, the fluoropropene composition may beused as a replacement for older generation refrigerants (e.g., R404A,R502) to provide a more environmentally friendly composition. In someembodiments, the fluoropropene composition may be a hydrofluoroolefincomposition. In an embodiment, the fluoropropene composition includesfrom 99 mole percent to 99.99 mole percent of 1,3,3,3-tetrafluoropropene(HFO-1234ze)(E) and from 0.01 mole percent to 1.0 mole percent of2,3,3,3-tetrafluoropropene (HFO-1234yf). In another embodiment, thefluoropropene composition is a near azeotropic composition that issubstantially free of HFO-1234ze(Z). By substantially free, it is meantthat the fluoropropene composition contains less than about 1000 ppm,less than about 500 ppm and typically less than about 100 ppm,HFO-1234ze(Z).

In one embodiments, the inventive fluoropropene compositions can beblended with other fluorochemicals. This embodiment of the presentinvention relates to a refrigerant composition comprising the inventivenear azeotropic composition (e.g., HFO-1234ze(E) and HFO-1234yf) and atleast one compound selected from the group consisting of: HFC-1234ye,HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc,propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF₃SCF₃, CO₂, CF₃I and combinations thereof.

In some embodiments, the fluoropropene composition may be used in arefrigeration system. One embodiment of a refrigeration system includesan evaporator, a condenser, a compressor, an expansion device, and aheat transfer media. The heat transfer media includes the fluoropropenecomposition. The heat transfer media can further comprise at least onelubricant including those suitable for use with refrigeration orair-conditioning apparatus. Among these lubricants are thoseconventionally used in compression refrigeration apparatus utilizingchlorofluorocarbon refrigerants. Such lubricants and their propertiesare discussed in the 1990 ASHRAE Handbook, Refrigeration Systems andApplications, chapter 8, titled “Lubricants in Refrigeration Systems”,pages 8.1 through 8.21, herein incorporated by reference. Lubricants ofthe present invention may comprise those commonly known as “mineraloils” in the field of compression refrigeration lubrication. Mineraloils comprise paraffins (i.e. straight-chain and branched-carbon-chain,saturated hydrocarbons), naphthenes (i.e. cyclic or ring structuresaturated hydrocarbons, which may be paraffins) and aromatics (i.e.unsaturated, cyclic hydrocarbons containing one or more ringscharacterized by alternating double bonds). Lubricants of the presentinvention further comprise those commonly known as “synthetic oils” inthe field of compression refrigeration lubrication. Synthetic oilscomprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes),synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins.Representative conventional lubricants of the present invention are thecommercially available BVM 100 N (paraffinic mineral oil sold by BVAOils), naphthenic mineral oil commercially available under the trademarkfrom Suniso® 3GS and Suniso® 5GS by Crompton Co., naphthenic mineral oilcommercially available from Pennzoil under the trademark Sontex® 372LT,naphthenic mineral oil commercially available from Calumet Lubricantsunder the trademark Calumet® RO-30, linear alkylbenzenes commerciallyavailable from Shrieve Chemicals under the trademarks Zerol® 75, Zerol®150 and Zerol® 500 and branched alkylbenzene, sold by Nippon Oil as HAB22.

In one embodiment, the lubricant component can comprise those which havebeen designed for use with refrigerants and are miscible with thefluoropropene compositions (e.g., near azeotropic compositions) of thepresent invention under compression refrigeration and air-conditioningapparatus' operating conditions. Such lubricants and their propertiesare discussed in “Synthetic Lubricants and High-Performance Fluids”, R.L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, butare not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol,United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow(Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVEs).

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed. The amount of lubricant can range from about 1 to about50, about 1 to about 20 and in some cases about 1 to about 3 weightpercent of a refrigerant composition. In one particular embodiment, theforegoing refrigerant compositions are combined with a PAG lubricant forusage in an automotive A/C system having an internal combustion engine.In another particular embodiment, the foregoing refrigerant compositionsare combined with a POE lubricant for usage in an automotive A/C systemhaving an electric or hybrid electric drive train.

In one embodiment, a refrigerant composition comprises the inventivenear azeotropic composition, at least one lubricant and at least oneadditive which can improve the refrigerant and air-conditioning systemlifetime and compressor durability are desirable. In one aspect of theinvention, the foregoing refrigerant compositions comprise at least onemember selected from the group consisting of acid scavengers,performance enhancers, and flame suppressants.

In another embodiment, the fluoropropene composition may be used in aprocess to transfer heat. The process may include providing an articleand contacting the article with a heat transfer media including thefluoropropene composition. In some embodiments, the article may includeelectrical equipment (e.g., circuit board, computer, display,semiconductor chip, or transformer), a heat transfer surface (e.g., heatsink), or article of clothing (e.g., a body suit).

In another embodiment, the fluoropropene composition may be used in aprocess for treating a surface. The process may include providing asurface having a treatable material deposited thereon and contacting thesurface with a treatment composition including the fluoropropenecomposition. In some embodiments, the treatment composition maysubstantially dissolve the treatable material.

In another embodiment, the fluoropropene composition may be used in aprocess for forming a composition. The process includes providing asolute and contacting the solute with a solvent including thefluoropropene composition. In some embodiments, the fluoropropenecomposition may substantially dissolve the solute.

In another embodiment, the present invention relates to blowing agentcompositions comprising the fluoroolefin-containing compositions (e.g.,near azeotropic containing compositions), as described herein for use inpreparing foams. In other embodiments the invention provides foamablecompositions, and preferably polyurethane and polyisocyanate foamcompositions, and method of preparing foams. In such foam embodiments,one or more of the present fluoroolefin-containing compositions areincluded as a blowing agent in foamable compositions, which compositionpreferably includes one or more additional components capable ofreacting and foaming under the proper conditions to form a foam orcellular structure. Any of the methods well known in the art, such asthose described in “Polyurethanes Chemistry and Technology,” Volumes Iand II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y.,which is incorporated herein by reference, may be used or adapted foruse in accordance with the foam embodiments of the present invention.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition afluoroolefin-containing composition of the present invention; and (b)reacting the foamable composition under conditions effective to form afoam.

Another embodiment of the present invention relates to the use of thefluoroolefin-containing compositions as described herein (e.g., nearazeotropic compositions of HFO-1234ze(E) and HFO-1234yf), for use aspropellants in sprayable compositions. Additionally, the presentinvention relates to a sprayable composition comprising thefluoroolefin-containing compositions as described herein. The activeingredient to be sprayed together with inert ingredients, solvents andother materials may also be present in a sprayable composition.Preferably, the sprayable composition is an aerosol. Suitable activematerials to be sprayed include, without limitations, cosmeticmaterials, such as deodorants, perfumes, hair sprays, cleaners, andpolishing agents as well as medicinal materials such as anti-asthma andanti-halitosis medications.

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a fluoroolefin-containingcomposition as described herein to active ingredients in an aerosolcontainer, wherein said composition functions as a propellant.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole. Thetransitional phrase “consisting essentially of” is used to define acomposition, method that includes materials, steps, features,components, or elements, in addition to those literally disclosedprovided that these additional included materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention, especially the mode ofaction to achieve the desired result of any of the processes of thepresent invention. The term ‘consisting essentially of’ occupies amiddle ground between “comprising” and ‘consisting of’.

In the foregoing combinations of inventive embodiments, the nearazeotropic compositions can comprise, consist essentially of or consistof HFO-1234ze(E) and HFO-1234yf.

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

Example 1 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An Inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Johnson Mathey) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 1.

TABLE 1 % Z-ze added 0 7.5 10.9 Incoming compos 100/0 92.5/7.5 89/11245fa conversion (%) 71.2 69.3 72 Z-ze in product (%) 10.7 10.3 11.2 %recovered 245fa 28.8 28.4 24.9 % E-ze 60.5 60.3 63.9 % yield E-ze 60.565.3 71.7 % selectivity E-ze 85 94.2 99.7

Example 2

Example 2 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An Inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Guignet's green) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 2.

TABLE 2 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 69.9 71.8 Z-ze in product (%) 10.7 10.9 % recovered 245fa 30.1 25.1% E-ze 59.2 64 % yield E-ze 59.2 71.9 % selectivity E-ze 84.7 100

Example 3

Example 3 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Johnson Mathey) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 3.

TABLE 3 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 73 71.3 Z-ze in product (%) 11.4 11.0 % recovered 245fa 27.0 25.5 %E-ze 61.6 63.5 % yield E-ze 61.6 72.5 % selectivity E-ze 84 100

Example 4

Example 4 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Newport Cr) which had been prepared as follows. Chromic oxidein extrudate form, which was crushed and sieved to 12/20 mesh. Aftercharging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 4.

TABLE 4 % Z-ze added 0 10.7 Incoming compos 100/0 89.3/10.7 245faconversion (%) 72.2 70.2 Z-ze in product (%) 10.4 10.5 % recovered 245fa27.8 26.6 % E-ze 61.8 62.9 % yield E-ze 61.8 70.4 % selectivity E-ze85.5 100

Example 5

Example 5 demonstrates the dehydrofluorination of 245fa over fluoridedalumina in the presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) is filled with 10 cc (6.1 gm) of Al₂O₃catalyst (purchased from Sigma-Aldrich). Al₂O₃ in extrudate form, whichis crushed and sieved to 12/20 mesh. After charging the reactor tube,the temperature of the catalyst bed is raised to 300° C. and purged withnitrogen (30 cc/min) for 200 minutes. Then the flow of nitrogen isreduced to 60 cc/min and HF is fed at 20 cc/min for 60 minutes. Thetemperature is increase to 325° C. for 300 minutes. The flow of nitrogenis then lowered to 30 cc/min and the flow of HF is raised to 30 cc/minfor 30 minutes. The flow of nitrogen is then lowered to 12 cc/min andthe flow of HF is raised to 48 cc/min for 60 minutes. The flow ofnitrogen is then discontinued and the flow of HF is raised to 48 cc/minfor 30 minutes. The reactor temperature is then decreased to 250° C. for30 minutes. Afterwards HF is turned off and the reactor is purged with30 cc/min of nitrogen. The reactor temperature is then stabilized at300° C., the flow of nitrogen is turned off, and either CF₃CH₂CHF₂, orCF₃CH₂CHF₂ with varying amounts of Z-1234ze, is fed at 1.44 ml/hr.Contact time in the reactor is 45 seconds.

The CF₃CH₂CHF₂ is vaporized at 50° C. Part of the reactor effluent ispassed through a series of valves and analyzed by GCMS. Amounts forZ-1234ze, 245fa and E-1234ze are expressed as mole percent. Results aresummarized in Table 5.

TABLE 5 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 70 71 Z-ze in product (%) 11 11 % recovered 245fa 30 29 % E-ze 59 58% yield E-ze 59 65 % selectivity E-ze 84.3 100

Example 6

Table 6 discloses the reaction products of the dehydrofluorination of245fa over various catalysts in the presence of Z-HFC-1234ze (in mol %).

TABLE 6 Catalyst Unknown 143a 152a TFP 1234yf 1233xf JM 62-2 0.15% 0.13% 0.00% 0.01% 0.35% 0.03% LV 0.28% 0.14%  0.03% 0.02% 0.04% 0.00% JM-62-30.28% 0.14%  0.02% 0.02% 0.24% 0.04% Newport-Chrome 0.12% 0.13%  0.00%0.00% 0.92% 0.00% Catalyst E-1233zd Z-1233zd Z-1234ze E-1234ze E +Z-1234ze JM 62-2 0.88% 0.13% 11.17% 87.13%  98.3% LV 1.03% 0.15%  10.9%87.4% 98.3% JM-62-3 0.92% 0.14%    11% 87.2% 98.2% Newport-Chrome 0.92%0.11%  10.5% 87.3% 97.8%

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of catalyst(see Table 6). After charging the reactor tube, the temperature of thecatalyst bed was raised to 300° C. and purged with nitrogen (30 cc/min)for 200 minutes. Then the flow of nitrogen was reduced to 60 cc/min andHF was fed at 20 cc/min for 60 minutes. The temperature was increase to325° C. for 300 minutes. The flow of nitrogen was then lowered to 30cc/min and the flow of HF was raised to 30 cc/min for 30 minutes. Theflow of nitrogen was then lowered to 12 cc/min and the flow of HF wasraised to 48 cc/min for 60 minutes. The flow of nitrogen was thendiscontinued and the flow of HF was raised to 48 cc/min for 30 minutes.The reactor temperature was then decreased to 250° C. for 30 minutes.Afterwards HF was turned off and the reactor was purged with 30 cc/minof nitrogen. The reactor temperature was then stabilized at 300° C., theflow of nitrogen was turned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂with 10.5-11% of Z-1234ze, was fed at 1.44 ml/hr. Contact time in thereactor was 45 seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part ofthe reactor effluent was passed through a series of valves and analyzedby GCMS. Amounts for Z-1234ze, 134a, 152b, TFP, 1234yf, 1233xf,E-1233zd, Z-1233zd and E+Z-1234ze are expressed as mole percent. Resultsare summarized in Table 6.

Example 7

Table 7 shows the near azeotropic characteristic of variouscompositions, which can be produced by the method of the presentinvention, by measuring Delta P of vapor pressure in terms of percentchange. Delta P vapor pressure is the vapor pressure change at −25° C.after a 50% vapor leak wherein 50% of the vapor is removed.

TABLE 7 1234zeE/1234yf wt % Delta P % 99/1 0.45 99.1/0.9 0.40 99.2/0.80.36 99.3/0.7 0.31 99.4/0.6 0.28 99.5/0.5 0.22 99.6/0.4 0.19 99.7/0.30.13 99.8/0.2 0.09 99.9/0.1 0.04 99.91/0.09 0.04 99.95/0.05 0.0399.96/0.04 0.02 99.97/0.03 0.01 99.98/0.02 0.009 99.99/0.01 0.00599.9987/.0013  0.001

Example 8

Table 8 shows the cooling performance of various near azeotropiccompositions, which can be produced by the method of the presentinvention, by comparing cooling capacity and energy efficiency (COP) toHFO-1234ze(E). The data are based on the following conditions.

T_condenser=47.0 degC.

T_evaporator=7.0 degC.

subcool=12.0 K

superheat=3.0 K

compressor efficiency=0.7

Average Heat Exchanger Temperature Set Points

Superheat is included in refrigeration effect

cooling load=1.0 tonnes

compressor displacement=0.1 (m{circumflex over ( )}3/min)

TABLE 8 Capacity COP Cooling Rel to Rel to Capacity 1234ze 1234ze Mol %(kJ/m3) (%) COP (%) 1234ze 100 2111 100.0% 4.402 100.0% 1234ze/1234yf99.9/0.1 2112 100.0% 4.402 100.0% 1234ze/1234yf 99.7/0.3 2114 100.1%4.402 100.0% 1234ze/1234yf 99.5/0.5 2116 100.2% 4.402 100.0%1234ze/1234yf 99.1/0.9 2120 100.4% 4.401 100.0%

Example 8 illustrates that the inventive near azeotropic compositionsare effective for use as refrigerants and have refrigeration propertiesat least equivalent to HFO-1234ze(E).

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

While the invention has been described with reference to a preferredembodiment, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

What is claimed is:
 1. A composition refrigerant comprisingE-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene(HFO-1234yf), and additional compounds comprising1,1,1,3,3-pentafluoropropane (HFC-245fa), 3,3,3-trifluoropropene(HFO-1243zf), and 1,1,1,2,2-pentafluoropropane (HFC-245cb), whereinbased on the total fluoroolefin composition the amount of HFO-1234ze(E)is about 99 mole percent, the HFO-1234ze(Z) is present and in an amountup to 500 ppm, and the amount of HFO-1234yf is from 0.01 mole percent to0.9 mole percent.
 2. The refrigerant of claim 1 further comprising, asthe additional compounds, at least one of1-chloro-3,3,3-trifluoropropene (E) (HCFO-E-1233zd) and1-chloro-3,3,3-trifluoropropene (Z) (HCFO-Z-1233zd) wherein the amountof HFO-1234yf is from 0.01 up to 0.5 mole percent based on the totalfluoropropene composition.
 3. The refrigerant of claim 2, wherein therefrigerant comprises R-1233zd(E).
 4. The refrigerant of claim 2,wherein the refrigerant comprises R-1233zd(Z).
 5. The refrigerant ofclaim 2 including between 0.01 and 0.25 mole percent HFO-1233zd(Z) basedon the total fluoropropene composition.
 6. The refrigerant of claim 1wherein the refrigerant comprises at least one lubricant.
 7. Therefrigerant composition of claim 6 wherein the lubricant comprisespolyol esters (POE).
 8. The refrigerant of claim 6 wherein the lubricantcomprises polyalkylene glycols (PAG).
 9. The refrigerant of claim 1wherein HFO-1234yf is present in an amount from 0.01 to 0.5 mole percentand the refrigerant further comprises as one of the additional compoundsat least one of 1,1,1-trifluoroethane (HFC-143a) and 1,1-difluoroethane(HFC-152a), wherein 1,1,1-trifluoroethane (HFC-143a) is present in anamount of 0.05 mole percent to 0.25 mole percent, based on the totalfluoropropene composition.
 10. The refrigerant of claim 1 whereinHFO-1234yf is present in an amount between 0.2 and 0.8 mole percent andthe additional compounds of the refrigerant further comprise at leastone of pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane(HFC-134a), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), and1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).
 11. The composition ofclaim 10 wherein the refrigerant further comprises trifluoromethane(HFC-23), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane(HFC-134a), 1,1,1-trifluoroethane (R-143a), 1,1-difluoroethane (R-152a),1,1,1,3,3,3-hexafluoropropane (HFC-236fa), and1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).
 12. The refrigerant ofclaim 1 including between 0.01 and 0.5 mole percent HFO-1234yf based onthe total fluoropropene composition.
 13. The refrigerant of claim 1further comprising as the additional compounds one or more of1,2,3,3-tetrafluoro-1-propene (HFC-1234ye), difluoromethane (HFC-32),pentafluoroethane (HFC-125), 1,1,2-tetrafluoroethane (HFC-134a),1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a),fluoroethane (HFC-161) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)and the amount of HFO-1234yf ranges from 0.1 to 0.5 mole percent.
 14. Arefrigerant comprising Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)),E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene(HFO-1234yf), 1,1,1,3,3-pentafluoropropane (HFC-245fa),3,3,3-trifluoropropene (HFO-1243zf) and 1,1,1,2,2-pentafluoropropane(HFC-245cb), and further comprising at least one member selected fromthe group consisting of 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye),difluoromethane (HFC-32), pentafluoroethane (HFC-125),1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane(HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane(HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane(HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea),1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,3,3-pentafluorobutane(HFC-365mfc), propane, n-butane, isobutane, 2-methylbutane, n-pentane,cyclopentane, dimethylether, CF₃SCF₃, CO₂, and CF₃I, wherein based onthe total fluoroolefin composition, the amount of HFO-1234ze(E) is atleast about 99 mole percent, the amount of HFO-1234ze(Z) is greater thanzero and up to about 500 ppm, and the amount of HFO-1234yf is between0.01 mole and 0.9 mole percent.
 15. A refrigerant comprisingZ-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)),E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene(HFO-1234yf), 1,1,1,3,3-pentafluoropropane (HFC-245fa),3,3,3-trifluoropropene (HFO-1243zf) and 1,1,1,2,2-pentafluoropropane(HFC-245cb) and at least one member selected from the group consistingof 1,1,1-trifluoroethane (R-143a), 1,1-difluoroethane (R-152a),2-chloro-3,3,3-trifluoropropene (R-1233xf),1-chloro-3,3,3-trifluoropropene (E)(E-1233zd),1-chloro-3,3,3-trifluoropropene (Z) (Z-1233zd),1-chloro-2,3,3,3-tetrafluoroprop-1-ene (1224yd),3-chloro-1,1,3,3-tetrafluoroprop-1-ene (1224zc),2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (1326mxz),1,1,2-trichlorotrifluoroethane (HCFC-113), difluoromethane (HFC-32),trifluoromethane (HFC-23), and 1,1,1,4,4,4-hexafluorobutane(HFC-356mff), wherein based on the total fluoropropene composition, theamount of HFO-1234ze(E) is at least about 98 mole percent, theHFO-1234ze(Z) is present but in an amount of less than 1000 ppm, and theamount of HFO-1234yf is between 0.01 mole and 0.5 mole percent.
 16. AnHFO-1234ze composition based on the total fluoropropene compositionconsists essentially of about 99 mole percent HFO-1234ze(E), between0.01 and to 0.9 mole percent 2,3,3,3-tetrafluoropropene (HFO-1234yf),between greater than zero and up to 500 ppm HFO-1234ze(Z), and thebalance of the composition including 1,1,1,3,3-pentafluoropropane(HFC-245fa), 3,3,3-trifluoropropene (HFO-1243zf),1,1,1,2,2-pentafluoropropane (HFC-245cb), optionally one of HCFO-1233xfand HFO-1233zd, and at least one member selected from the groupconsisting of 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye),difluoromethane (HFC-32), pentafluoroethane (HFC-125),1,1,2,2-tetrafluoroethane (HFC-134), 1 1,1,1,2-tetrafluoroethane(HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane(HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane(HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea),1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,3,3-pentafluorobutane(HFC-365mfc), propane, n-butane, isobutane, 2-methylbutane, n-pentane,cyclopentane, dimethylether, CF₃SCF₃, CO₂, and CF₃I, and optionally alubricant.
 17. A refrigerant composition comprisingE-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)) and2,3,3,3-tetrafluoropropene (HFO-1234yf), and additionally 1,1,1,3,3-pentafluoropropane (HFC-245fa), 3,3,3-trifluoropropene (HFO-1243zf),1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,2,3,3-tetrafluoro-1-propene(HFC-1234ye), difluoromethane (HFC-32), pentafluoroethane (HFC-125),1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a),1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161) and1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), wherein based on the totalfluoroolefin composition the amount of HFO-1234ze(E) is at least about99 mole percent, the HFO-1234ze(Z) is present and in an amount betweengreater than 0 and less than about 500 ppm, and the amount of HFO-1234yfis between 0.1 mole and 0.9 mole percent.
 18. A composition refrigerantcomprising a blend of (1) E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E))Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)) and2,3,3,3-tetrafluoropropene (HFO-1234yf), and (2) pentafluoroethane(HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a),1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1-trifluoroethane(HFC-143a) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), whereinbased on the total fluoroolefin composition the amount of HFO-1234ze(E)is at least about 99 mole percent, the HFO-1234ze(Z) is present in anamount that is greater than zero and less than about 500 ppm, and theamount of HFO-1234yf is between 0.01 mole and 0.9 mole percent.
 19. Acomposition refrigerant comprising a blend of (1)E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),Z-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)) in an amount greater than 0and up to about 500 ppm, 2,3,3,3-tetrafluoropropene (HFO-1234yf) and (2)pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a),1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1-trifluoroethane(HFC-143a), 1,1-difluoroethane (HFC-152a) and1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), wherein based on the totalfluoroolefin composition the amount of HFO-1234ze(E) is at least about99 mole percent and the amount of HFO-1234yf is between 0.1 mole and 0.5mole percent.